CA1039444A

CA1039444A - Method for preparing polyalkenamers

Info

Publication number: CA1039444A
Application number: CA194,409A
Authority: CA
Inventors: Tatyana L. Jufa; Tamara Y. Chepurnaya; Boris D. Babitsky; Kim S. Soloviev; Tamara T. Denisova; Vitaly A. Kormer; Irina M. Lapuk; Mark I. Lobach; Nadezhda P. Simanova
Original assignee: Individual
Current assignee: Individual
Priority date: 1973-03-09
Filing date: 1974-03-07
Publication date: 1978-09-26
Also published as: GB1466695A; DE2411208A1; BE850574Q; CS170037B1; FR2237917A1; DD112137A1; IT1007377B; US3933777A; FR2237917B1

Abstract

Abstract A method for the preparation of polyalkenamers which con-sists in the polymerization with ring opening of the alicyclic unsaturated compounds in the presence of a catalyst comprising three components:
a) a compound of a transition metal of Groups IV-VIII of the Periodic System;
b) a compound of a metal of Groups I-VI of the Periodic System; and c) quinone or its halogen derivative or an acid halide of sulfur-containing acid having the general formula RkSOnQt wherein R is halogen, aryl, alkyl, nitro- or amino-group; S can be sulfur; O represents oxygen; Q
stands for halogen; k=0-1; n=1-2; t=1-2.
The aforespecified component "c)" makes the catalyst more active.

Description

1~D3~40~4 This invention relates to methods for the preparatio~ of polyalkenamer~ which ma~ ~ind wide applicatio~ i~ the ~ynthe~
tic rubber industry. Vulcanizates of the ~ai~ polyalkenamers have good physical characteristics a~d elasticity and also good resista~ce to ~ro~t.
~ here is k~own a method of prep~ring polyalkenamers b~
polymexization with ring opaning o~ alicyclic unsaturated com-pounds i~ the presence of a catalytic system comprising a -allylic compleæ of a tra~sition metal o$ Group~ IV-VIII
of the Periodic Sys~em having the general ~ormula:
k / m wherei~
~1 is a metal of Groups IV-VIII of the Periodic System7 X can be halo~en 9 acetate, ~ydro~y1, alkoxyl, c~anide, cyclopenta~ienyl, acet~lacet~nate, alkyl- and ar~lsul~`o-nate group.
represents carbonyl, cyclopentadien~l, cyclooctadiene, be~zene, cycloheptatriene, cyelododecatriene, trihaloge~-pho~phine, triphe~ylpho~phine and trlpheDylph~sphite, A desig~ates a ~ all~lic ligand of the general formula R1 R4 R1 R2 ~3 1' 1' I
(I) C ~ C - C or (II) C - C ~ a R2 l3 15 (CH2)q wherein R17R2, R3,R4,R5 are hydrogen , halogen j alkyl, cycloalkyl and ~ roup ar~l having from 1 to 10 carbon atoms;
n=0-4; p-0-3; k-0-6; m=1-29 q=1-9 take~ in combinatio~ with compounds o~ metals o~ Groups I-VI o~
the Periodic System of the general formula d Ze/g Pf wherei~
M3 I~ a metal o~ Groups I-VI o~ the Periodic System7 U can be hydro~en, halogen and alkoxy-group~
represe~ts halogen~ aliphatic and aromatic sub~tituent havi~g ~rom 1 to 18 carbon atom~;
P stands for ether or amine;
d=0-4; e=0-4; g=1-2; ï=0-2 (U.S.A.patent 3,~60,369) ~ here i~ also the known method for the preparation of pol~-alkenamer~ which provldes the use o~ a catalyst consisting of the salt of mol~bdenum or tung~te~ having the general ~'ormula / M2 Ra Xb / Yc wherei~
molybdenum~ tung~ten;
R can be h~lo~en, aliphatic and aroma~ic substitue~ having ~rom 1 to 10 ~arbon a~om~;
X repre~e~ts haloge~a¢yl-, alko~y-, arylo~y- a~d acet~l-` ac~to~ate group;
Y ~tand3 for ether or amine;
a=0-6; b-0-6; c=0-3 a+b=a vale~ce of M2 metal taken in combination with an or~anic compound or h~dride of a

- 2 -~.0394~
metal of Groups II-III of the Periodic System in the presence of an activator which can be an oxygen-containing compound having 0-0 or 0-H bond (U.S.A. patent 3,449,310)~
The disadvantage of the known methods is the relatively low activity of the catalysts used.
It is the principal object of the present invention to provide a method ensuring a considerable gain in the rate of polymerization and the increased yield of polyalkenamers.
According to the invention there is provided a method for the preparation of a polyalkenamer by homopolymerization comprising polymerizing, with ring opening, an alicyclic unsaturated monomerhaving from 4 to 5 and from 7 to 12 carbon atoms and from 1 to 4 double bonds in a ring in the presence of a catalyst comprising a) i) a transition metal compound of the general formula / An Ml ~p L~ /m wherein Ml is a transition metal of Groups IV-VIII of the Periodic ; System, X is a ligand selected from the group consisting of halogen, acetate, hydroxyl, alkoxy, cyanide, cyclo-pentadienyl, acetylacetonate, alkyl- or arylsulfonate group, L is a ligand selected from the group consisting of carbonyl, cyclopentadienyl, cyclooctadiene, benzene, cycloheptatriene, cyclododecatriene, trihalogenphosphine, : triphenylphosphine and triphenylphosphite, A is a ~~-allylic ligand of the general formula Rl R4 Rl R2 R3 (I) C... C -.- C or (II) C --- C C
R2 R3 R5 (CH2)q ~1~39~44 wherein Rl, R2, R , R , R are selected from the group consist-ing of hydrogen, halogen, alkyl, cycloalkyl, aryl having from 1 to 10 carbon atoms;
n=0-4; p=0-3, k=0-6; m-1-2, q=l-9 or ii) a transition metal compound of the general formula / M2RaXb/ YC
wherein M2 is molybdenum or tungsten;
R is a halogen, aliphatic or aromatic ligand having from 1 to 10 carbon atoms;
X represents acyl-, alkoxy-, aryloxy- or acetyl-acetonate group;
Y stands for ether or tertiary amine;
a=0-~; b=0-6, c=0-3;
a+b=the valence of M2 metal, b) a metal compound having the general formula / M3 Ud Ze/g Pf wherein . 20 M3 is a metal of groups I-VI of the Periodlc System, U is hydrogen, halogen or alkoxy--group;
Z represents halogen or an aliphatic or aromatic radical having from 1 to 18 carbon atoms, ; P is an ether or amine ligand, d=0-4, e=0-4; g=1-2; f=0-2;
d+e=the valence of M3 metal;
c) an activator selected from the group consisting of quinones and halogenated quinones.

39~44 said polymerization being carried out in an inert solvent at a temperature of -50C to 80C, the molar ratio of said monomer to the transition metal compound being from 100-20,000 : 1.

The activator c) may be, for example, ortho-benzo-quinone, para-benzoquinone, naphthaquinone, anthraquinone and phenanthrenequinone, the halogenated quinones include the fluoro-, chloro-, bromo- and iodo-derivatives of these quinones.
The ring of the alicyclic unsaturated monomer may be substituted by alkyl-, aryl-, aralkyl-, alkaryl-, acyl, alkoxy-group having from 1 to 10 carbon atoms and also halogen atoms.
The ring of an alicyclic compound may have one or more such groups or atoms.
The polymerization is suitably carried out in aninert solvent such solvents include aliphatic, alicyclic and aromatic hydrocarbons and their halogenated derivatives and ether, the polymerization is suitably continued for 0.1 up to 10 hrs. at a temperature of from -50 to +80C.

~03944~

Thc moli0r ri~tio of the catalyst components a:b:c ma;y be 1 :/o.1-50~:/o.1--10/.
'l~he proposed method ~or the prapiaration of polyal~enamer~
is realized in the ~ollowing mi~nnerO
Polymerizi~tio~ is ¢arried out as continuous or batch pxo-ce~s in reactors o~ conve~tio~al type which are usually used e.g~for the poLymerization of butadie~e or i~oprene~ The aforespeci~ied components may be intr~duced in a solution simulti~neoui31y or one after i~not~er. ~he resultant polymer mi~y be ~solated ~rom a solution by i~ny conve~io~al methodt e~g.
by preciplta~ion wi~h ethi~nol.
'l`he above ide~ti~ied catalytic sy~tem3 u~ed in th~ poly~
merizatio~ aocordlng to the proposed method iare chRracterized by increased activity as compiared with that of th~ known cata-lyst~.
~ ho employment o~ quinones, their halogen derivati~es a~d acid halides of ~ulfur-containing acid as an activator allows one to obtai~ a considerable galn in the rate o~ polymerization and alæo to increase the conversio~ o~ monomers.
The a~or~specified activators are easil~ available commer-cial products. With the help o~ the propo~ed method well reproducible results Gan be obt~ned.
For a better understandin~ of the present invention tho proposed method will now be described by way of illustration in the following examplesO
~ x a m P 1 e Into a 100-ml., round-bottomed,three-~ecked ~lask are /

~ 39~
placed u~der argon 45ml. of tolue~e, 10go 0~ cyclopente~e, 15x~o 5 mole of WC16 in 4 ml. of toluene, 15x~o 5 mole of para-benzoquinone in ~ ml. of toluene, and 6x1o~~ mole oY
ethylaluminium dichloride. The polymerizatio~ is carried out at a temperature of 0C for a period of 2 hours. The polymer is obtained in a yield o~ 6.5g. (65% o~ the theoretical amount). The polymer contains the theoretical amount o~
douhle bond~; its intrin~ic viscoæity /~ J=3.5 dl./~. (in benz~o~at 25~).
1~ ~
The pol~m~rization is carried out a~ descrlbed in Example 1, e~cept that tungsten oxytetrachloridetdiisobutylaluminium chlo-ride/tetrachloroquinone in the mol~r ratio of 1/1/0.25 i~ u~ed as the catalyst system. As a monomer cyclooctens is used.
After 1 hour the polymer is obtai~ed i~ a yield oX 93%
o~ the theoretical amou~t; it~ intrinsic visco~ity /~ /= 2.05 dl.Jg. (in benzene9 at 25C).
_x a m P l e 3 ~ he polymerization i3 carried out as described in Example 1, except that hexaphe~o~ytungst@n/totr~h~ltinJt~Eafl~oroquino~é
(the molar ra~io 1/2/0~5) in a chlorob~zene ~olution is used a~
the catalyst ~ystèm. As a monomer cyclobutene i~ used.
After 5 minute~ the polymer is obtained in a yield o~100~0 of the theoretical amount; its intrinsic viscosity ~ J=3~2 dl./g. (in benzene, at ~5C).

~039444 The polymerizatisn is carried out as described in Exampla 1, e~cept that chloroet~oxytungsten pe~achloridefdiethylzin~Jb~nzo quinone in a benzene 501ution i~ used as the catal~t sy6tem. As mo~omer cis,trans-cyclodecadiene-1,5 is used.
After 4 hours the pvlymer is obtained in a yield o~ 72% o~
the theoretical amou~t; its intrinsic viscosity J~ /=1.65 dl~/g. (in benze~e, at 25C).
E x a m p 1 e 5 ~ he polymerization is carried out as described in ~ample 1, except that dio~o~acetylacetonate)molybdenum/diethylaluminium chloride/1.4-naphtaquinone in a cyclohexane solution i5 used as the catalyst system. As a monomer 3-phenylcyclooctene i8 used.
: A~ter 8 hours the polymer i5 obtained in a giald of 47%
of the theoretical amount; its int:ri~sic viscosity /~ ~=1.25 dl./g. (in benzene, at 25C).
x a m ~ l e 6 ~ he polymerization is carried out as described in Example 1, except tha~ MoO~ dipyrid~lJHAlCl2-trimethylami~e/dibromo-quino~e (the molar ratio 1/4/1) i~ a haptane solution i~ used as the catalyst 6ystem. As a o~omer 1-meth~lcycloo¢tadiene-195 iS u~ed.
~ fter ~ hour~ tha pol~mer is obtained i~ a yield o~ 56% o~
the theoretical amount; its intrinsic visco~ity J~ /=2.2 dl./g.
(in benzene, at 25C).

~3944~
Example 7 The polymerization is carried out as described in Example 1, except that tungsten hexachloride/butyllithium/
chloranil (the molar ratio 1/3/1) in a toluene solution is used as the catal~st system.
The catalyst complex is prepared in the presence of the monomer, cis, trans, trans-cyclododecatriene-1,5,9~ After 2 hours the polymer is obtained in a yield o 78% of the theoretical amount; its intrinsic viscosity / ~ / = 1.57 dl/g.
(in benzene, at 25C~.
Example )3 Into a 50-1., stalnless steel autoclave fitted with a stirrer and a jacket are fed 301. of benzine, 61. of cyclopentene, 13.5xlO 3 mole of tungsten hexachloride, 13.5xlO 3 mole of para-benzoquinone, and 54xlO 3 mole of ethylaluminium dichloride. The polymerization is carried out at a temperature of -5C for a period of 3 hours.
The polymer is obtained in a yield o~ 70%. The intrinsic VlSCOSity of the polymer / ~/ = 3 dl/g. ~in benzene, at 25 C), its glass transition temperature Tg=102 C.
.

_g_ ~()39~4 Example 9 The polymerization is carried out as described in Example 1, except that tungstenoxytetrachloride/diisobutyl-aluminium chloride/benzenesulfinylchloride in the molar ratio of 1/1/0.25 is used as the catalyst system. As a monomer cyclooctene is used. After 1 hour the polymer is obtained in a yield of 85% of the theoretical amount; its intrinsic viscosity / ~/=1.9 dl./g. (in benzene, at 25C)o Example 10 The polymerization is carried out as described in Example 1, except that tris(phenoxy) molebdenum chloride/
H2AlI. diethyl ether/thionyl chloride (the molar ratio 1/2/1) in a heptane solution is used as the catalyst systemO AS
a monomer cyclobutene is used.
After 0.5 hour the polymer is obtained in a yield of 92% of the theoretical amount, its intrinsic viscosity / ~/=2.85 dlO/g. (in benzene, at 25C).
Example 11 The polymerization is carried out as described in Example 1, except that tungsten hexafluoride~tetraethyltin/
sulfuryl chloride (~3~4~
(the molar ratio 1/2/0.25) in a chlorobenzene solution iæ used as the cataly~t system. As a monomer cis, trans-cyclodecadiene-1~5 is used.
A~ter 5 hour~ -the polymar is obtained in a yield of 65~o of tha theoretical amoun-t; its intrinsic viscosi-ty ~ 1.95 dlo/g~ (in benzene, at 25~
E x a m P l e ~ he polymerization is carried out as described in Example 1, except that chloroetho~ytun~ten pentachloride/butyllithium/para-brom~benze~e sulfochloride (the molar ratio 1~2fO.5) in a benzene solution i9 used a~ the catal~st system. As a ~onomer 3-phe~yl-c~clooctene i~ usedO
~ ter 10 hour~ the pol~mer is obtained in a yield of 52~o o~ the theoretical amount; its intrin~ic viscosity ~ /=1.07 dl./g~ (in benzene, at 25C)~
L~
as ~ he polymorization is carried out deecribed in ~ample 1, except that the combination dio~oacetylacetonate mol~bdenumJ
trlethylalumin~umJp-ami~obenze~esulfochloride (the molar ratio 1/~J1) in a toluene solution is used as the catalyat system.
As a monomer 1-methylcyclooctadiene-1,5 is used.
~ fter 1.5 hour the polymer is obtained in a yield of ~5~o of the theoretical amount; its intrinsic viscosity /~ ~=1.7 dl./g~ (in benzene, at 25C).
E~
~ he polymerization is carried out as described in ~xample 19 ~L~39d~4~
except that tungsten hexachlori~e/diethylaluminium chloria~m-x~lene-4 sulfochlori~e (the molar ratio 1J~/1) in a chloroben-zene solution is used a~ the ca-talyst system. As a monomer Ci9, trans~ trans-c~rclododecatriene-1~5~9 is used.
After 5 hours the polymer is obtained in a yield of 65~o o~ the theoretical amount; its intrinsic viscosity ~ /=2 dl./g.
(in benzene, at 25C).
E x a m ~ 1 e .
~ he polymerization is carried out as dsscribed in Example 17 except that cyclohexenesul~ochloride is used a~ ths activator.
After 0.5 hour the polymer is obtained in a ~ield o~ 58% of the theoretîcal amount; its intrinsic viscosi-ty ~ /=2.20 dl./g. (in benzene, at 25;~).
x a m p 1 e ~
~ he polymerization is carried out as described in ~xample 1, except that propanesulfochloride is used a~ the activator .
After 1 hour the polymer is obtained in a yield of 62%
of the theoreti¢al amount; its i~trinæic ViSCGSity /~ /=2.02 dl~/g. (in benzene, at 25C).
' il a) Into a 100-ml.,round-bottomed,three-necked fla~k are placed 65 ml. of benzene, 0.15x10 3 mole of tetra(~ pen~enyl)tungsten i~ 2 ml. of benzone, 0.15x~0 3 mole o~ benzo~ui~one in 2 mlc .
of benzene, 0.30~0 3 mole of aluminium bromido i~ 1 ml. o~
be~zene a~d 10g. (15~0 2 mole) of cyclopentene.
The pol~merizàtion i~ carried out at temperature of 0C

~ 12 -. .

io394~9L
~or a period of 1 hourO The polymer is obtained in a yield of 8.~ g~ (85% OI the theoretical a~nount)O q~he polymer contains the theoretical amount of double bo~ds.
~ he i~trinsic viscosity of the polymer /~ ~=2.5 dl./g.
(i~ benzene, at 25C~, b) The polymerizatio~ of cyclopanetene is carried out in the absence o~ the activator. Into a reaction ~las~ are placed 0.375x~0-3 mole of tetra~ crotyl)tu~g~ten,0075x~0~3 mole of alumi~ium bromide, 7.7 ~. (11g~0 2 mole) o~ cyclopentene. After a period of 5 hours at a temperature of 30~ the polymer is obtained in a yield o~ 90% tthe check runj.

,, , , S~:
~`i The polymerization is carried out as aescribad in Example ~P, e~cept that tetra(~ -allyl)zirco~ium~dichloroquinone/tunæste~
hexachloride in the molar ratio o~ ~I/1J4 is used as the cata-lyst system.
~ter 1.5 hour the psl~mer is obtai~ed in a yield of 73%
o~ the theoretical amount; it~ intr~nsic viscosity /~, /=1~,78 dl~/go ~iIl benzeno, at 25C).

The polymerizatien is carried out as described irl Example , except that tetra(~ -methall~l)tuDgstenJtetraiodo~ o~eJ
diethylethoxyaluminium(the molar ratio 1/1.5/4) i~ a t~luene solutio~ is u~ed as the catal~st system. As a monomer ci~-cy~lo-oetene i8 used. A~ter 1 hour the polymer is obtained in a yield of 92% of the theoretical amount. Its intrinsic vi~cosity /~ /=3.0 dl./g. (i~ benzene, at 25C)~

- ~3 -9~44 E x a m P 1 e ~
~ he polymerization is carried out as described in ~æample 48, excopt that cyclopen-tadie~ylcobalt dicarbonyl/1~4-naphtaquino-n3/tungsten he~a~luoride (the molar ratio 1/1/2) in a heptane solution is u~ed as -tho catalyst s~stem. After 0.5 hour the polymer is obtained in a yield o~ 95~0 o~ the theoretical amount1 its intrin~ic viscosity /~ /-4.2 dl./~. ~in benzene~
~ at 25C).
: E x a m P 1 o -~Z
~ he polymarization i~ carried out a~ described in Example ~, except that cyclopentadienyltantalum tetracarbonyVtriethyl-alumi~ium/chloranil (the molar ratio 1/0.5/4) in a tolue~e solutio~ is u~e~ as the cataly~t system. As a monomer 1-methyl-cyclooctadie~-1,5 is used. After 5,5 hours the polymer i5 obtained i~ a ~ield of 40~0 o~ ~he theoratical amount; its intrinsic viscosity /~ 47 dl4/~o (in benzene, at 25C)~
x a m P l a .
: ~he polymerization i~ carried out as des~ribed in hXample , except that Re2(C0)10/o-benzoquinone/tetraphcnyltin ~the molar ratio 1/1/3) in a benzene solution is ussd a~ the catal~3t sy~tem. As a mo~omer Ci9~ trans, trans-cyclododecatri-ene~1,5,9 is usea. After 5 hours the pol~mer i8 obtained in a yield of 56% of the theoretical amount; its intrin~i¢ v~sco~
sity f~ /=1,27 dl.~g. (in be~ene, at 25C)~
.. .

~0394~

E ~ a m p 1 e The polymerization is carried out as described in ~xample , except that ~is~ -all~l)nickel/pne~gltung~ten pentachloride/
2,5- dibromoquinone ~the molar r~tio 1/4J1,5) in a cy¢lohexane ~olution is used as the catalyst ~ystem. As a monomer 3-phe~yl-c~clooctene is used. After 4 hour~ the polymor i~ obtained in a yield of 51~o of the theoretical amount; it~ intrinsic vi~cosity /~ /=1738 dlo/g~ (in benzene, at 25~C)~

~ he polym~ri~ation is carried out as de~cribed in Example ~9 except that tri~ crotyl)tungsten chloride/benzo~uinone/a complex of chlorala~ ~ith trimethylamine (the molar ratio 1/1/2 in a chlorobenzene ~olution is used as the catalyæt s~tem.
A~ a monomer ci~, trans-c~clodecad:Lene-1,5 is used. After 6 hour~ the pol~mer is obtained in a ~ield of 73% o~ the theore-tical amount; its intrinsic vi~cos:ity ~ 1,85 dl./g. (in benzene, at 25~
aJ

a) Into a 100-ml~,round-bottomed,three-necked ~lask are placed 65 ml. of benzene~ 0.15x~0 3 mole of tetra~ -methallyl)tung-~ten i~ 2 ml. of bsnze~e~ 0~15x~0 3 mole of thionyl chloride in 2 ml~ of benzene~ 0.6~0 3 mole of aluminium bromide in 1 ml.
of benzene and 10~ (15x~0 2 mole) o~ cyclopentene. Th~ poly-merization is carried ou~ at a temperature of 0C for a period 0~5 hour. 'l'he polymer i~ obt~in~d in a ~ield o~ 8,7 g (87% o~
the theoretical amount). ~he polymer contains the theoretical ~0;~9gL~4 ~mou~t o~ double bonds; its intrinsic viscosity /~ /=223 dl~
(in benzene, at 25C)~
b) ~he polymerization of c~clopen-tene is carried out in the absence of the activator, the monomer to ~ -comple~ ratio being 300/1~ A~ter a period of 5 hours at a temperature of 30C the polymer i~ obtained in a yield of 90% (the check run).
x a m p 1 e ~
~he polgmcrization is carried out as described in hxample , e~cept that tetra(~ -allyl)zirkonium/benzenesulfochloride/
tu~gste~ h~xachloride in the ratio of 1/1/4 is uaed as the cataly~t sys-tem. After~ hour the polymer is ob~ained i~
a yield of 75% of the theoretical amount; its intrinsic visco~ity /~ 80 dle/g~ (in b~nzene , at 25C~.
~1 ( ~he polymerlzation i~ carried out a~ de~cribed,in Example -26, except that tetra(~ -pe~tenyl)tun~sten/benze~esul~inyl chlo-ride/diethyletho~y aluminium (the ~olar ratio~1l1,5/4) in a tolue~e solution is used as the catalys~ s~tem. A~ a monomer cis-cycloocten~ is used. ~fter 1 hour the polymer is obtai~ed : in a ~ield o~ 90% of the theoretical amount; its intrinsic ~isco-~ity t~ ,o dl./g. (in bsnzene, at 25C).
~ ` ~8 ~ he polgmeriæatio~ is carried out as described in 13æa~pla ~, except that cyclopelltadienylcobalt dicarbo~yl/æul~uryl chloride/tungsten hexa~luoride (the molar ratio 1/1/2) i~ a heptalle solution is used as the catalyst system. As a mo~Qo~er 1¢~394~
cyclobutene ~s used. After Op5 hour the polymer is obtai~ed in a yield o~ 95% of the theoretical amount; its intrinsic visco-sity /~ J-4,5 dl~/g~ (in benze~e~ at 25VC).
E I ~
~ he polymerization is caxried out as described in Example ~, except that cyclopentadienyltantalum tetracarbonyl~para-bromobenz~nesulfochloride/ethylaluminium dichloride (the molar ratio 1/1,5/~) in a chlorobenzene solution is us~d a~ the catalyst s~stem. ~5 a monomer cyclooctadiene-1,5 is used. ~ter 1,5 hour the polymer i~ obtained in a ~ield of 73% of the thaoretical amount; its intrinsic viscosity /~ /_1985 dl./g.
(in benzene, at ~5C).
~3 E x a m P 1 e ~
'l'he polymerization i~ carried out a5 described in Example , except that dirhenium d~cacarbonyl/para-~m;nobenzenesulfo-chloride/phengltu~gsten pentachloride (the molar ratie 1JO,5/2 in a toluena solution i6 used as the catalyst sy~tam. AB a monomer cyclope~tene is u~edO ~fter 2 hours the polymer is obtained in a yield of 5O% of the theoretical amount; it~ intri~-sic ~iscosity /~ /=1,75 dl./g. (in b~nzene, at ~5 L4L~L~.~L 3 , ~he polymerization iB carried out as descri~ed in Examplo i~, except that tris (9f -allyl) tu~g~t en chloride~thionyl chlo-ride/a complex o~ chloralan with trimethylami~e (the molar ratio 1/1/4) in a cyclohe~ane solution is used as the catalyst ~ystem.
As a monomer cis, trans, trans-cyclododecatriene-1~5,9 iB usedO

After 1 hour the polymer is obtained in a yield o~ 8t~ o~ the theoretif~al amount; its iIrtrinsic viscosity /~ ~=1,2 dl./g.
(in benzeneq at 25C)o .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A method for the preparation of a polyalkenamer by homopolymerization comprising subjecting an alicyclic unsaturated monomer having from 4 to 5 and 7 to 12 carbon atoms and from 1 to 4 double bonds in the ring to polymerization with ring open-ing in the presence of a catalyst containing three components:
a) a compound selected from the group of i) transition metal compounds comprising .pi. - complexes of transition metals having the general formula / AnM1 Xp Lk/m wherein M1 is a transition metal selected from groups IV-VIII of the Periodic System;
X is a ligand selected from the group consisting of halogen, acetate, hydroxyl, alkoxyl, cyanide, cyclopentadienyl, acetylacetonate, alkyl sulfonate and arylsulfonate;
L is a ligand selected from the group consisting of carbonyl, cyclopentadienyl, cyclooctadiene, benzene, cycloheptatriene, cyclododecatriene, trihalogenphosphine, triphenylphosphine and triphenylphosphite, A is a .pi.-allylic ligand having the general formula (I) or (II) wherein R1, R2, R3, R4, R5 are ligands selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl and aryl having from 1 to 10 carbon atoms;
n=0-4; p=0-3; k=0-6; m=1-2; q=1-9;
and ii) transition metal compounds of the general formula /M2RaXb/Yc wherein M2 is molybdenum or tungsten;
R is a ligand selected from the group consisting of halogen, aliphatic and aromatic radicals having from 1 to 10 carbon atoms;
X represents a ligand selected from the group consisting of halogen, acyl, alkoxy-, aryloxy- and acetylacetonate groups;
Y is a ligand selected from the group consisting of ether and amine;
a=0-6; b=0-6; c=0-3;
a+b= the valence of M2 metal;
b) a compound of a metal selected from Groups I-VI of the Periodic System having the general formula /M3 Ud Ze/g?Pf wherein M3 is a metal selected from Groups I-VI of the Periodic System;
U is a ligand selected from the group consisting of hydrogen halogen and alkoxy-group;
Z represents a ligand selected from the group consisting of halogen, aliphatic and aromatic ligands having from 1 to 18 carbon atoms;
P is a ligand selected from the group consisting of ether and amine;
d=0-4; e=0-4; g=1-2; f=0-2;
d+e = the valence of M3 metal; and c) an activator selected from the group consisting of quinones and halogenated quinones said polymerization being carried out in an inert solvent at a temperature o-f -50°C to 80°C; the molar ratio of said monomer to the transition metal compound being from 100 - 20,000:1.

2. A method according to claim 1, wherein the molar ratio of catalyst components a:b:c is 1:0.1-50:0.1-10.

3. A method according to claim 1, wherein said inert solvent is selected from the group consisting of hydrocarbons, halogenated hydrocarbons and ethers.

4. A method according to claim 2, wherein said inert solvent is selected from the group consisting of hydrocarbons, halogenated hydrocarbons and ethers.

5. A method according to claim 1, 2 or 3, wherein said polymerization is continued for 0.1 to 10 hours.

6. A method according to claim 4, wherein said poly-merization is continued for 0.1 to 10 hours.

7. A method according to claim 1, 2 or 3, wherein said activator c) is selected from the group consisting of ortho-benzoquinone, para-benzoquinone, naphthaquinone, anthra-quinone and phenanthronequinone.

8. A method according to claim 1, 2 or 3, wherein said activator c) is a fluoro-, chloro-, bromo- or iodo derivative of a compound selected from the group consisting of ortho-benzoquinone, para-benzoquinone, naphthaquinone, anthraquinone and phenanthrenequinone.

9. A method according to claim 1, 2 or 3, wherein said monomer is selected from the group consisting of cyclo-butene; cyclopentene; cyclooctene; ciscyclooctene; and 3-phenylcyclooctene.

10. A method according to claim 1, 2 or 3, wherein said monomer is selected from the group consisting of cyclo-octadiene-1,5; 1-methylcyclooctadiene-1,5; cis,trans-cyclo-decadiene-1,5; and cis, trans, trans-cyclododecatriene 1,5,9.